Non-halogenated insulation with high oxygen index

ABSTRACT

The invention features in synergistic combination a new chemistry for fabricating wire and cable insulation and heat-shrinkable tubing and an irradiation process for providing the insulation with both increased tensile strength and increased elongation. 
     The chemistry utilizes a polycondensation-type process wherein a hydrophobic olefinic terpolymer base material having 3% or less carboxyl groups and a hydrophilic flame retardant filler material containing hydroxyl groups is linked to a silicone material containing silanol groups. 
     The insulation is further characterized by an oxygen index in excess of 50.0, resulting from high loadings of the fire retardant filler material, generally in excess of 200 parts by weight of the total material weight.

FIELD OF THE INVENTION

The present invention relates to a new non-halogenated wire andheat-shrinkable tubing insulation article having superior elongation andtensile strength as well as flame retardancy, and more particularly toan insulation featuring a non-halogenated system whose composition andphysical properties are achieved by a new synergy of advanced chemistryand irradiation processing.

BACKGROUND OF THE INVENTION

It has been known that superior insulating construction materials suchas tiles and wall boards can be achieved by a polycondensation processwhereby carboxyl groups forming part of an olefinic base are linked withsilanol groups contained in a silicone material. Additionally, thesilanol groups are linked with hydroxyl groups contained in a hydratedfire retardant filler to provide an insulation composition thattolerates large inclusions of the filler material. Such a process isdisclosed and described in European patent application publication No.EP 0 333 514 A1.

While the process claimed that the cross-linking had allowed for theinclusion of larger amounts of fire retardant filler materials into theinsulative composition, it was soon discovered that these compositionscould, not be processed into wire insulation of commercial quality.

One of the drawbacks of the chemistry was that the compositions taughtby the subject patent application could not be easily extruded.

Another difficulty with the new insulative compositions was theircharacteristically sub-standard commercial tensile strength, elongationand flexibility.

It was soon determined that the increased cross-linking of thesecompositions, while improving the fire retardancy by reason of providingfor increased filler loadings, nonetheless was overly binding thepolymer chains. Thus, flexibility and elongation were impaired. Suchoverbinding, while useful for tiles and wall construction materials,which are not commercially affected by the reduced flexibility andelongation, is not useful for wire and cable insulation applications.

The present invention reflects the discovery that commercial gradeinsulation for wire and cable, particularly plenum wire and cable andheat-shrinkable tubing, can be fabricated by appreciably reducing thecross-linking of the components of the polycondensation process.

The chemistry of the aforesaid patent application utilized olefinic basematerials containing 6% carboxyl groups by weight. This amount of thecarboxyl groups is too high a percentage for fabricating commercialgrades of wire insulation.

The present invention has determined that the viable range of carboxylgroups should be approximately below 3% by weight and preferably about1% by weight of the base material.

In addition, while the prior application stressed the need to includedialdehydes to promote the cross-linking of the compositionalcomponents, the present invention reflects the discovery that they aredetrimental to the processing of the insulation extrudate. Thedialdehydes generally increase the viscosity beyond workable extrusionlimits. Also, the dialdehydes reduce the temperatures at which theextrusion can be accomplished, thus further increasing the workingviscosity, and further impairing the processability of the resultantcomposition, Compositions containing the dialdehydes were found to causethe extrusion heads to rupture due to increased pressure and viscosity.The prior application teaches the necessity for the inclusion of thedialdehydes, but that is because the formulations set forth thereinrelate primarily to construction materials and not to wire insulation.

The prior patent application further teaches the inclusion of anethylene propylene elastomer in wire insulation compositions. Theseterpolymer blends were illustrative of the preferred wire insulationcompositions, but subsequent testing revealed that they provided wireinsulation with only marginal physical properties.

The current invention features a true terpolymer system rather than ablended terpolymer system. The terpolymers of the invention comprise acarboxylated ethylene vinyl acetate, without the inclusion of theelastomer, in order to improve the flexibility and the amount of fillerthat can be introduced into the system.

In addition to the changed chemistry, the invention subjected the newcompositions to electron beam irradiation in order to improve thetensile strength, and to allow generally higher loadings of the flameretardant filler materials.

Normally, when greater amounts of filler materials are employed, thetensile strength and elongation decrease. Irradiation often improvestensile strength, but has never been found to increase the elongation.The present invention has shown that without the silanol groupings, theresultant composition will not show an increase in elongation afterirradiation, as expected.

However, this invention incorporates the discovery that there is asynergy between the new chemistry and the irradiation, wherein thecombination of the two processes (i.e., new chemistry and irradiation)provides for both an increase in tensile strength and in elongation.

This dual increase is valid for greater than 200 parts by weight of theinclusion of a hydroxyl-containing filler material into the terpolymersystem.

Thus, the present invention has produced a new flame retardant wire andcable insulation with higher loadings of hydrated flame retardantfillers beyond those limits depicted in the aforementioned patentapplication. The effect of this new insulation on flame retardancy isdramatic, wherein the oxygen index for the new formulations is about200% greater than the best wire and cable polycondensation formula.

Furthermore, the present invention has introduced the higher fillerloadings without impairing the physical characteristics of thecomposition, whereby commercial grade insulation for a non-halogenatedwire and cable is now feasible for the first time at these higher fillerloadings.

The present invention features a non-halogenated composition for wireand cable and heat-shrinkable tubing insulation having superior flameretardancy, with oxygen indices approaching 70.0 or better. Theinventive insulation is further characterized both by increased tensilestrength and by increased elongation after irradiation, a resultheretofore unknown in the prior art.

SUMMARY OF THE INVENTION

In accordance with the present invention, there is provided anon-halogenated insulation composition suitable for heat-shrinkabletubing, wire and cable, and plenum wire capable of passage of therigorous UL910 plenum test, and whose insulation product has increasedtensile strength and increased elongation.

The insulation is formed by irradiating a terpolymer compositioncomprising an ethylene vinyl acetate base material containing carboxylgroups. The ethylene vinyl acetate comprises approximately 100 parts byweight of the total composition, and the carboxyl groups comprise nomore than approximately 3% by weight of the base. To the ethylene vinylacetate is added a hydroxyl-containing fire retardant filler of greaterthan 200 parts by weight, and a silicone material comprising silanolgroups, generally between 15 to 30 parts by weight. The vinyl acetatemoiety is approximately between 25 to 30% by weight of the basematerial.

The oxygen indices of the formulations produced by this invention areextremely high, illustrating their vastly superior flame retardancy.

The composition is chemically formed by a polycondensation-type processwherein the carboxyl groups of the hydrophobic ethylene vinyl acetatelink with the silanol groups of the silicone material, which also linkwith the hydroxyl groups of the hydrophilic flame retardant filler.

The irradiation of the composition in addition to the new chemistryprovides a synergistic result, wherein both the tensile strength and theelongation increase, thus allowing still higher loadings of the flameretardant filler, such a result being heretofore unknown in the priorart.

The tensile strength of the insulation will range from approximately2,000 psi to 1,000 psi, and is preferably greater than 1,500 psi.

The elongation will vary in a range of approximately from 450% to 370%.

The hydroxyl-containing fire retardant filler is preferably a magnesiumhydroxide, although other hydrated and hydroxyl-containing substances,such as aluminum trihydrate, are within the scope and purview of theinvention.

It will be observed that the hydrated filler loadings of this inventionare approximately 300% or more greater than those illustrated in theprior art polycondensation formulations. The result of this vastlysuperior formulation is the achievement of greatly improved flameretardancy as illustrated by the oxygen indices ranging fromapproximately 42.0 to 72.0.

The objectives and advantages of this invention will become moreapparent and will be better understood with reference to the followingdetailed description.

DESCRIPTION OF THE PREFERRED EMBODIMENT

Generally speaking, the invention features a synergistic combination ofa new polycondensation-type process for formulating wire and cable andheat-shrinkable tubing insulation and an irradiation process to providethe new plenum insulation with vastly superior flame retardancy andphysical strength and elongation.

The composition features a hydrophobic olefinic terpolymer system withhydrophilic flame retardant filler loadings greater than 200 parts byweight.

The irradiation process in combination with the new formulation of thisinvention has for the first time increased both the tensile strength andthe elongation of the composition.

Normally, only the tensile strength would be expected to increase withirradiation, while the elongation percentage would decrease in value.

While the prior art teachings encourage a strong polycondensationreaction with carboxyl groups of the terpolymer system in a range ofgreater than 3% by weight, increasing all the way to 20% by weight ofthe base material, the present invention de-emphasizes the cross-linkingreaction by drastically reducing the carboxyl groups to approximatelybelow 3% by weight, and preferably to about 1% by weight of its basematerial.

Contrary to the prior art teachings, the use of a dialdehyde to enhancethe chemical reaction is omitted to decrease the viscosity of thecomposition in order to improve the extrusion process. This omission notonly improves extrusion, but allows extruding to be performed at highertemperatures of about 300 degrees F.

The present invention also eliminates the need for inclusion of acarboxylated elastomer, such as ethylene propylene, thus changing thecharacter of the system from that of a terpolymer blend to that of atrue (single component) terpolymer.

The following Tables 1a and 1b feature a comparison of polycondensationformulations with components expressed in parts by weight of the totalcomposition. Control sample is a prior art formulation including both aglyoxal (dialdehyde) and an ethylene propylene (elastomer). It will beobserved that the hydroxylated filler loading is only 112.5 parts byweight, and the oxygen index is only 33.0, after irradiation.

The ranges of hydrated filler loadings and oxygen indices for thepresent inventive formulations show vast superiority over the prior artformulation, called the control sample.

                  TABLE 1a                                                        ______________________________________                                                        Sample No.                                                    Ingredients  Control  190-39-1 224-20-1                                                                             224-20-4                                ______________________________________                                        EEA 3330     37.5                                                             EVA 1830     31.25                                                            Elvax 4260            100.0    100.0  100.0                                   Elastomer    31.25                                                            Silicon Coupler                                                                            15.0                                                             A-172                 2.0                                                     SR-350                6.0                                                     SFR-100                        17.5   16.3                                    Zinc Stearate         2.0      2.0    2.0                                     Glyoxal      1.88                                                             ATH          112.5                                                            Kisuma 5B Mg(OH).sub.2                                                                              225.0    270.0  225.0                                   TiO.sub.2    5.0                                                              Zinc Borate  15.0                                                             Stabilizers  0.625    7.0      7.0    7.0                                     Before Irradiation                                                            Tensile Strength                                                                           2100 psi          1421 psi                                                                             1487 psi                                Elongation    80%              436%   473%                                    After Irradiation                                                             Tensile Strength                                                                           2614 psi 2020 psi 1709 psi                                                                             1850 psi                                Elongation   133%     347%     463%   520%                                    Oxygen Index*                                                                              33       53.1     49.1                                           ______________________________________                                         *Tested in accordance with ASTM D2863                                    

                  TABLE 1b                                                        ______________________________________                                                      Sample No.                                                      Ingredients     224-26-3 224-26-4   224-26-5                                  ______________________________________                                        Elvax 4260      100.0    100.0                                                Elvax 260                           100.0                                     SFR-100         20.4     22.6       17.5                                      Zinc Stearate   2.0      2.0        2.0                                       Kisuma 5B MG(OH).sub.2                                                                        315.0    350.0      270.0                                     Stabilizers     7.0      7.0        7.0                                       Before Irradiation                                                            Tensile Strength                                                                              1201 psi 1052 psi   496 psi                                   Elongation      373%     373%       460%                                      After Irradiation                                                             Tensile Strength                                                                              1525 psi 1173 psi   840 psi                                   Elongation      426%     370%       490%                                      Oxygen Index*            71.7       47.35                                     ______________________________________                                         *Tested in accordance with ASTM D2863                                    

SR-350 is a trimethylolpropane trimethacrylate made by the Sartomer Co.of West Chester, Pa.

SFR-100 is a silicone fluid made by General Electric Co. of Waterford,N.Y.

Kisuma 5B is a hydrated fire retardant containing approximately 97%magnesium hydroxide, made by the Kyowa Chemical Industry Co., Ltd.,Osaka, Japan.

Elvax 4260 is an ethylene/vinyl acetate/acid terpolymer made by DuPontCorp. of Wilmington, Del.

The elastomer (ethylene propylene terpolymer) was made by Exxon ChemicalCo.

EAA 3330 is made by Dow Chemical under the tradename Primacor.

EVA 1830 is manufactured by CIL of Canada.

Elvax 260 is an ethylene vinyl acetate copolymer manufactured by DuPontCorp. of Wilmington, Del.

All of the inventive formulations were fabricated by means of thefollowing typical example, which included irradiation by an electronbeam to impart radiation in the range from 5 to 20 Mega Rads, andpreferably 10 Mega Rads.

EXAMPLE

Each of the ingredients of the aforesaid formulations were weighed andthen added to a Banbury type intensive mixer. Each formulation was mixeduntil the polymer fluxed and the incorporation of the hydrated fillersyielded a homogeneous mass.

The composition was then converted into pellets, which were extrudedonto a 20 AWG copper conductor. The thickness of the insulativecomposition was 0.030', producing a wire sample.

The wire samples were then tested for tensile strength and elongationusing standard apparatus for this procedure.

After obtaining the tensile strength and elongation, identical sampleswere irradiated to a dose of 10 Mega Rads.

These irradiated samples were also tested for tensile strength andelongation, to provide the data in Tables 1a and 1b, as illustrated.

In order to better understand the new chemistry of this invention, asample was also formulated without the use of a silanol-containingsubstance, as shown in Table 2 below. This sample was irradiatedsimilarly to the samples in Tables 1a and 1b with the result that theirradiation only improved the tensile strength, but not the elongation.This demonstrates that the new chemistry in combination with theirradiation process is necessary to provide the inventive result.

                  TABLE 2                                                         ______________________________________                                                       Sample No.                                                     Ingredients      223-20-6 224-26-6                                            ______________________________________                                        Elvax 4260       100.0    100.0                                               Stabilizers      7.0      7.0                                                 Hydrated Alumina*                                                                              291.0    270.0                                               SR-350           16.7                                                         Zinc Stearate    2.0      2.0                                                 SFR-100          0        17.5                                                Before Irradiation                                                            Tensile Strength  637 psi 1332 psi                                            Elongation       113%     156%                                                After Irradiation                                                             Tensile Strength 1010 psi 1402 psi                                            Elongation        93%     176%                                                Oxygen Index**   42.6     48.65                                               ______________________________________                                         *Note:                                                                        Two different grades of hydrated alumina were used for these two samples:     Micral 932 SL (22420-6); and Alcoa 710 (22426-6).                             **Tested in accordance with ASTM D2863                                   

Since other modifications and changes varied to fit particular flameretardant and physical characteristics will be apparent to those skilledin the art, the invention is not considered limited to the exampleschosen for purposes of disclosure, and is considered to cover allchanges and modifications which do not constitute departures from thetrue spirit and scope thereof.

Having thus described the invention, what is desired to be protected byLetters Patent is subsequently presented by the appended claims.

What is claimed is:
 1. A fire retardant, non-halogenated wire and cableinsulation, featuring increased tensile strength and elongationresulting from irradiation of a composition including:a) an ethylenevinyl acetate base resin comprising approximately 100 parts by weight ofthe total composition, and containing carboxyl groups belowapproximately 3% by weight of said base resin; b) a silicone materialcontaining silanol groups and comprising approximately between 15 to 30parts by weight of the total composition; and c) a flame retardanthydrated filler material containing hydroxyl groups and comprisinggreater than 200 parts by weight of the total composition, said silanolgroups linking both with the carboxylic groups of the ethylene vinylacetate base resin, and the hydroxyl groups of the flame retardanthydrated filler material, said silanol groups having sufficient linkagewith said carboxyl groups and said hydroxyl groups to provide saidcomposition with a high, flame retardant, oxygen index, but havinginsufficient linkage capability to allow for extrusion of saidcomposition into wire and cable insulation.
 2. The fire retardant,non-halogenated wire and cable insulation of claim 1, wherein said vinylacetate moiety is approximately between 25% to 30% of the base resin. 3.The fire retardant, non-halogenated wire and cable insulation of claim1, wherein said fire retardant hydrated filler material comprisesmagnesium hydroxide.
 4. The fire retardant, non-halogenated wire andcable insulation of claim 1, wherein said fire retardant hydrated fillermaterial comprises hydrated alumina.
 5. The fire retardant,non-halogenated wire and cable insulation of claim 1, having an oxygenindex greater than 40.0.[...]. .Iadd., tested in accordance with ASTMD2863.Iaddend..
 6. The fire retardant, non-halogenated wire and cableinsulation of claim 1, wherein elongation is in excess of 100%.
 7. Thefire retardant, non-halogenated wire and cable insulation of claim 1,wherein tensile strength is approximately in a range of between 1,000and 2,000 psi.
 8. The fire retardant, non-halogenated wire and cableinsulation of claim 1, wherein elongation is in excess of 100% andtensile strength is greater than 1,000 psi.
 9. The fire retardant,non-halogenated wire and cable insulation of claim 1, wherein saidcarboxyl groups comprise approximately 1% of said base resin.
 10. A fireretardant, non-halogenated wire and cable insulation, comprising anirradiated composition whose tensile strength and elongation have bothincreased as a result of said irradiation, said composition including:a)an olefinic terpolymer base material comprising approximately 100 partsby weight of the total composition, and containing carboxyl groups belowapproximately 3% by weight of said base material; b) a silicone materialcontaining silanol groups and comprising approximately between 15 to 30parts by weight of the total composition; and c) a flame retardanthydrated filler material containing hydroxyl groups and comprisinggreater than 200 parts by weight of the total composition, said silanolgroups linking both with the carboxylic groups of the olefinicterpolymer base material, and the hydroxyl groups of the flame retardanthydrated filler material via a polycondensation process, said silanolgroups having sufficient linkage with said carboxyl groups and saidhydroxyl groups to provide said composition with a high, flameretardant, oxygen index, but having insufficient linkage capability toallow for extrusion of said composition into wire and cable insulation.11. The fire retardant, non-halogenated wire and cable insulation ofclaim 10, wherein said olefinic terpolymer comprises an ethylene vinylacetate whose vinyl acetate moiety is approximately between 25% to 30%of the base material.
 12. The fire retardant, non-halogenated wire andcable insulation of claim 10, wherein said fire retardant hydratedfiller material comprises magnesium hydroxide.
 13. The fire retardant,non-halogenated wire and cable insulation of claim 10, wherein said fireretardant hydrated filler material comprises hydrated alumina.
 14. Thefire retardant, non-halogenated wire and cable insulation of claim 10,having an oxygen index greater than 40.0.[...]. .Iadd., tested inaccordance with ASTM D2863.Iaddend..
 15. The fire retardant,non-halogenated wire and cable insulation of claim 10, wherein tensilestrength is greater than 1,000 psi and elongation is increased to morethan 100%.
 16. The fire retardant, non-halogenated wire and cableinsulation of claim 10, wherein elongation is in excess of 100%.
 17. Thefire retardant, non-halogenated wire and cable insulation of claim 10,wherein tensile strength is approximately in a range of between 1,000and 2,000 psi.
 18. The fire retardant, non-halogenated wire and cableinsulation of claim 10, wherein said carboxyl groups compriseapproximately 1% of said base material.
 19. A fire retardant,non-halogenated wire and cable insulation formed by a polycondensationprocess comprising, an irradiated composition whose tensile strength andelongation have both increased as a result of said irradiation, saidcomposition including:a) a hydrophobic olefinic terpolymer base materialcontaining carboxyl groups below approximately 3% by weight of said basematerial; b) a hydrophilic flame retardant hydrated filler materialcontaining hydroxyl groups and comprising greater than 200 parts byweight of the total composition; and c) a silicone material containingsilanol groups, said silanol groups linking both with the carboxylicgroups of the hydrophobic olefinic tarpolymer base material, and thehydroxyl groups of the hydrophilic flame retardant hydrated fillermaterial via said polycondensation process, said silanol groups havingsufficient linkage with said carboxyl groups and said hydroxyl groups toprovide said composition with a high, flame retardant, oxygen index, buthaving insufficient linkage capability to allow for extrusion of saidcomposition into wire and cable insulation.
 20. The fire retardant,non-halogenated wire and cable insulation of claim 19, wherein saidolefinic terpolymer comprises an ethylene vinyl acetate whose vinylacetate moiety is approximately between 25% to 30% of the base material.21. The fire retardant, non-halogenated wire and cable insulation ofclaim 19, wherein said fire retardant hydrated filler material comprisesmagnesium hydroxide.
 22. The fire retardant, non-halogenated wire andcable insulation of claim 19, wherein said fire retardant hydratedfiller material comprises hydrated alumina.
 23. The fire retardant,non-halogenated wire and cable insulation of claim 19, having an oxygenindex greater than 40.0.
 24. The fire retardant, non-halogenated wireand cable insulation of claim 19, wherein elongation is in excess of100%.
 25. The fire retardant, non-halogenated wire and cable insulationof claim 19, wherein tensile strength is approximately in a range ofbetween 1,000 and 2,000 psi.
 26. The fire retardant, non-halogenatedwire and cable insulation of claim 19, wherein said carboxyl groupscomprise approximately 1% of said base material.
 27. A method offabricating insulation, comprising the steps of:a) linking carboxylgroups contained in a hydrophobic olefinic terpolymer base material withsilanol groups contained in a silicone material; b) linking silanolgroups of said silicone material additionally with hydroxyl groupscontained in a hydrophilic fire retardant material, whereby saidsilicone material is linked to both said hydrophobic and hydrophilicmaterials; and c) irradiating the linked hydrophobic and hydrophilicmaterials to increase both tensile strength and elongation.
 28. Themethod of claim 27, wherein said linking results from apolycondensation-type reaction.
 29. The method of claim 27, wherein saidhydrophilic flame retardant material is in excess of 200 parts by weightof the total weight of materials.
 30. The method of claim 27, whereinsaid hydrophilic flame retardant material is in excess of 300 parts byweight of the total weight of materials.
 31. The method of claim 27,wherein the linked materials are irradiated with approximately between 5and 20 Mega Rads of radiation.
 32. The method of claim 31, wherein thematerials are irradiated with approximately 10 Mega Rads of radiation.33. The method of claim 27, wherein said insulation has an oxygen indexgreater than 40.0.[...]. .Iadd., tested in accordance with ASTMD2863.Iaddend..
 34. The method of claim 27, wherein said insulation hasan elongation greater than 100% and a tensile strength greater than1,000 psi. .[.35. A non-halogenated flame retardant insulation having anoxygen index in the approximate range of between 40 and 72..]. .[.36.The non-halogenated flame retardant insulation of claim 35, wherein saidoxygen index is greater than approximately 50..].